Alkylation process



sti-tuents of saturated character. processes, a. charge comprising a mixtureof a Patented Sept. 10, 1946 UNITED STATES PATENT OFFICE ALKYLATION PROCESS William A. Stover, Woodbury, N. ,L, ,assignor to Socony-Vacuum Oil Company, Incorporated, a

corporation of New York .No Drawing. Application February 24, .1944, Serial No. 523,727

15 Claims. 1 This invention relates generally to the alkylation -of parafiinic hydrocarbons with olefinic hydrocarbons, and isv more particularly concerned with the production of high-octane motor fuel by the catalytic alkylation of paraflinic hydrocarbons with oleflnic hydrocarbons.

eration. costs their essential feature being that in the course of treating the materials, the olefinic hydrocarbon-s produced inthe earlier stages of the process, are eventually polymerized to gasoline. Accordingly, hydrocarbon gases may be passed along with cracking stock or naphtha through acrackingstill to crack and polymerize such gases to gasoline simultaneously with the cracking or reforming, orparaifinic hydrocarbon gases may be separatelycracked to: olefinic hydrocarbon gases and thesegases are subsequently passed with naphtha through a polymerizingand reforming still. Insome instances,;the processes involve the use of catalysts for facilitating the cracking and/or polymerization operations,

.It is also well knownin the art, to combine pa-raffinic hydrocarbons directly with olefinic hydrocarbons by. processes broadly called, alkylation processes, tGgPI'Od-UCBJITlQtfll fuels having con- In alkylation parafiinic hydrocarbon, called the paraffinic reactant, and an olefinic hydrocarbon, called the olefinic reactant, is subjected to high tempera ture and pressure-to produce asaturated alkylate product. Sincethese temperature, pressure, etc.,

conditions, or briefly, :alkylating conditions, also cause polymerization of the olefinic reactant, it is necessary to maintain a relatively low concentration of the wolefinic reactant in the charge. The only limit to the pressure used appearsto be the feasibility ofmaintaining high pressures. .On-the other hand, the temperature used ,is. .limited by degradation of the hydrocarbon reactants inthe charge to low molecular weight hydrocarbons, and the occurrence of side reactions, including poly merization of the olefinic reactant, under high temperature conditions, that substantially reduce the purity of the product obtained.

Alkylation may be 'condu'ctedat high temperatures and pressures, on the order of over 900 F. and over 4000 pounds per square inch gaug respectively; or maybe conducted in the presence of alkylation catalysts, at lower temperatures and pressures, thereby assuring a high yield of desired alkylate by avoiding extensive degradation of the reactants, the occurrence of side andsecondary reactions, and appreciable polymerization of the olefinic reactant. The two methods are known as thermal alkylation and as catalytic. alkylation, respectively.

Several methods are known for the catalytic alkylation of isoparafiinic hydrocarbonswith olefinic hydrocarbons. For instance, it isknown to alkylate isoparafiinic hydrocarbons with olefinic hydrocarbons in the presence of sulfuric acid,

phosphoric acid, metal phosphates, metal halides, activated clays and the like, as catalysts. In these catalytic alkylation processes, the hydrocarbon reactants form with the alkylation cata lysts, a heterogeneous system during the alkylation operations. Since'under alkylation conditions, the catalytic activity of the alkylation catalysts appears to be predicated upon contact between the catalysts .and the gaseoushydrocarbon reactants at theinterfaces therebetween, in these processes, the catalysts are used in amounts varying between about 10% and 200% by weight, on the charge, depending on the catalyst used. Due to these comparatively high amounts, where possible, recovery and regeneration of the catalysts have been proposed. This, of course, involves high initial and operation costs. Further, it is also known that-certain substances called promoters, promote the catalytic action of these alkylation catalysts. Accordingly, several processes have been proposed wherein small amounts of these promoters, on the order of about 1% to 3% by weight on the charge, are added to the catalysts to promote their alkylation catalytic activity.

A copending application, Serial Number 502,018, filed September 11, 1943, is directed to the process of alkylating paraflinic or isoparaffinic hydrocarbons with olefinic hydrocarbons, which comprises contacting a paraffinic or isoparaifinic hydrocarbon and an --olefinic hydrocarbon in a reaction zone under alkylating conditions, with small amounts of what has been termed therein, .a homogeneous gaseous phase alkylation catalyst which consists essentially of materials that form with the hydrocarbon reactants, a single, homogeneous gaseous phase under the alkylating conditions of the reaction zone. The alkylating con. ditions of the process of this copending application, comprise a broad temperature range of about AlCls, H2SO4, and the like.

3 590 F. to about 850 F., preferably, about 650 F. to about 825 F., and pressures of at least 500 pounds per square inch gauge, preferably, at least 1500 pounds per square inch gauge.

Another copending application, Serial Number 502,813, filed September 1'7, 194:3,is directed to the process of alkylating isobutane with propylene, which comprises contacting isobutane with propylene in a reaction zone under closely controlled alkylating conditions, with promoter or small amounts of the homogeneous gaseous phase catalysts broadly disclosed in the copending aplication referred to hereinabove, the closely controlled alkylating conditions including a temperature range of about 750 F. to about 850 F., pref erably, about 775 F. to about 825iF., and pres sures of at least 2500 pounds per square, inch gauge. In the alkylation of isobutane with propylenein the presence of homogeneous'g'ase'ous phase alkylation catalysts, it was found that the 'alkylate obtained included constituents that are entirely different from the constituents of the hydrocarbon alkylate obtained in the alkylation of isobutane with propylene in the presence of known heterogeneous alkylation catalysts, i. e.,

Thus, when heterogeneous alkylation catalysts are used, 2,3-dimethylpentane and 2,4-dimethylpentane are important constituents of the hydrocarbon alkylate obtained. On the other hand, triptane or 2,2,3- trimethylbutane, 2,2-dimethy1pentane, and 2- methylhexan are the predominant constituents of the hydrocarbon alkylate, when gaseous phase homogeneous alkylation catalysts are employed.

lEn this copending application, the formation of these three compounds was postulated as follows:

' isobutane Propylene 2-methylhexane :From a motor fuel standpoint, the 2,2-dimethyl- 'pentane produced by the first reaction, has an "octane number of about 80 CFR motor method; "the triptane produced by the-second reaction has an octane'number'of well over 1.00, and the 2- methylhexane obtained in the third reaction, has an octane number of about 4.5. In view of the foregoing, in the manufacture of higli octane :motorfuel by the alkylation of isobutane with propylene, 'alkylation conditions that favor the :prdductionoftriptane obviously are preferable. EFurther,.'since neohexane which may be produced by the alkylation of isobutane with ethylene, has :an octane number of 93.4, and since 2,3-dimethyl- :pentane and'ZA-dimethylpentane which are the. predominant constituents of the alkylate ob- 'tained in the alkylation of isobutane with pro- .pyleneinthe presence of heterogeneous alkylavtion catalysts, have octane numbers of 89 and 82,-respectively, th importance of the alkylation of isobutane with propylene in the presence of homogeneous gaseous phase catalysts under alkylation conditions that favor the production of triptane, is manifest. It was also found that in actual practice, it was impossible to obtain triptane exclusively, appreciable amounts of 2,2-dimethylpentane and 2-methylhexane being always formed.

The specific classes of homogeneous gaseous phase alkylation catalysts claimed in the abovenoted copending applications, are organic halides, and, more particularly, organic chlorides and organic bromides.

I have found that carbon dioxide is a suitable homogeneous gaseous phase alkylation catalyst; and that isoparaffinic or parafiinic hydrocarbons .may be efiiciently alkylated with olefinic hydrocarbons to produce high yields of high-octane gasoline, by using relatively small amounts of carbon dioxide.

I have also found that carbon dioxide is a suit able homogeneous gaseous phase catalyst in the catalytic alkylation of isobutane with propylene under the controlled alkylating conditions described in copending application, Serial Number 502,813, filed September 17, 1943, referred to hereinbefore.

It is an object of the present invention to provide an efficient process for catalytically alkylating isoparafiim'c or parafiinic hydrocarbons with olefinic hydrocarbons. Another object is to provide an efficient process for catalytically alkylating either normal parafi'inic hydrocarbons or'isoparaffinic hydrocarbons with olefinic hydrocarbons to produce high yields of high-octane motor fuel, A more specific object is to provide a process for catalytically alkylating isobutane with propylene to produce high yields of high-octane motor fuel. A very'important object is to afford a process capable of carrying out the above objects by using relatively small amounts of carbon dioxide as alkylationcatalyst. Otherobjects and advantages of the present invention will be come apparent to those skilled in the art from the following description.

Broadly stated, my invention provides afprocess for alkylating parafiinic or isoparamnic hydrocarbons, particularly isobutane, with olefinic hydrocarbons, particularly propylene, which comprises contacting the parafiinic and olefinic hydrocarbons in. gaseous phase and in a reaction zone under alkylating conditions, with an alkylation i catalyst consisting essentially of carbon dioxide. 7 a V An important feature of the process of the present invention is the fact that, contrary to the known catalytic alkylation processes of the prior art which are onlycapable of alkylating isoparaffinic hydrocarbons, myprocess is capable of al- -ky1ating either normal paraffinic or isoparafiinic hydrocarbons with substantially equa1 ease.

-Anoth er important feature of the process of the present invention is the relatively low temperature that may be used. As a result, degradation of the hydrocarbon reactants in the charge to low molecular weight hydrocarbons and the a pronounced occurrence of side reactionsinclud- Ling polymerization of the olefinic reactants, are substantially completely avoided. Consequently, in my process, Iobtain high yields of a high grade product that is almost entirely paraflinic in nature and'is substantially free from impurities.

.A very important feature of the present inven tion is the'fact that, contrary to known catalytic processes of the prior art in .which the hydrocarbon reactants being processed form with the aaomse between, it: iollows that the catalytic efficiency of a. given catalyst increases; with the. increase in area. of: interfacial contact, other variables remaining constant. Hence, since the catalyst of myrprocess inherently furnishes the greatest possible interiacial. contact? between the catalyst and-the. hydrocarbon reactantsunder the alkylating conditions of the. reaction zone, efficientucata, lytic activity with a concomitant high yield of high grade alkylate is achieved using relatively smallamounts .of carbon dioxide.

Inview of:the. foregoing, an'operation feature of. the. process of the. present invention that. is

of .consi'derablepractical importance, is that rel,

atively small amountsof carbon dioxideare used as alkylation. catalyst. These amounts and. the cost are so small that the catalyst may be discarded feasibly, therebyobviating recovery and regeneration problems and eliminating high initial and operation costs.-

A most important feature of the present invention is that: high yields of high-octane motor fuel areobtainedby alkylating isobutane with propylene in the presence of carbon dioxide.

The amount-of carbon dioxide used inmyprocess varies between about 3% and about 20%, and preferably, between about 6% andabout 9%, with respect to the volume of the total charge of hydrocarbon-reactants. It must be noted, however, that larger amounts of carbon dioxide may be employed if desired, although no additional advantages result therefrom.

The paraffinic and olefinic hydrocarbonsto be used in my process may be derived from any suitable source, as is well known in the art, and may be'used either inthe-pure state or in admixture with other constituents not undesirable. The parafiimc and olefinic hydrocarbonsusually employed in the preferred operation of manufacturi-ng motor fuels, will be the normally gaseous paraffinic hydrocarbons, except methane and ethane, and the normally gaseous olefinic hydrocarbons, as is well understood in the art. Here again my process has a distinct advantage over many of the prior art processes in that the olefin-ethylene may be used for alkylatingthe paraffinic hydrocarbons. It is well known that ethylene cannot be used in many catalytic processes, including the sulfuric acid process, whereby the supply of available olefinic hydrocarbons is restricted. Therefore, an important aspect of the present invention is the fact that butane, for instance, may be alkylated with ethylene.

Aconventionaland prefered source of parafiinic and olefinic hydrocarbons is the fixedgases. obtained around petroleum refineries. These fixed gases may furnish substantially all the desired paraffi nic and-olefinic hydrocarbons, or it may be necessary or desirableto obtain additionalsupplies, asis wellunderstood. Additional olefim'c hydrocarbons, if required, may beformed froma portion of the para-fiinic hydrocarbons. On the other hanch, additional ,paralhnic hydrocarbons may be admixed to increase: the concentration. of paraffinic hydrocarbons to adesired magnitude.

In carrying out my process, I use. temperatures varying between about 590 F. and about 850 F., preferably temperatures varying between about 650 F. and about 825. F. In the alkylation of isobutane with propylene, however, I have found, as disclosed in the copending application, Serial No. 502,813, filed September 17, 1943, that the best yields of desired alkylate are obtain-ed when the alkylation is conducted at temperatures fall ing within about 750 F; to about 850" Fz, and preferably, about 775 F. to about 825 F. The alkylate produced under these conditions contains no more than 5% of olefinic hydrocarbons and no aromatics so that the predominance of alkylation obtained thereby is a distinct feature of my process. Under appreciably higher temperature conditions, side reactions occur that substantially reduce the purity of the product obtained; Inthe alkylation of isobutane with propylene in accordance with the process of the present invention, it must be noted that'even within the preferred temperature range, side reactions occur that account for substantial portions of the totalalkylate.

The pressure to be used in my. process may vary from. about 50.0. pounds per square. inch to about 6000 pounds per square inch or more; and preferably from about-j 2500 pounds per square inch to about 6000 pounds per square inch for the alkylation of isobutanewith propylene, the most suitable pressure being more or less dependent upon the particular temperature involved. In general, the higher the pressure, the higher the yield of alkylate. Accordingly, the criterion for establishing an upper limit to the pressure range used is primarily the feasibility of maintaining such pressure.

In my process it is desirable, as in known isoparaffin-olefin alkylation processes, to-keep-the concentration of the alefinic reactant relatively low during the alkylation reaction, inorder to eliminate as much olefin polymerization as possible. Accordingly, it is advisable to maintain the olefin concentration in the charge below about 25% by volume, and preferably between about 7% and about 12% by volume.

Traces of water apparently haveno seriousill effects on the course of the reaction-in .thejprocess of my invention, and there is evidence to support the conclusion that small. amounts of water may be beneficial.

The alkylate-product that I obtain distills over a fairly large boiling range, but a greater part ofthe alkylate, usually from about to about distills in the boiling range of aviation gasolines. The iodine number of the aviation distillate is low, on the order of about 5 to 10. As mentioned hereinabove, the alkylate product con.- sists predominantly of branched parafiinic hydrocarbons.

Numerous experimental data could be adduced to indicate the results obtainable in accordance with the process of th present invention, but the folowing examples are sufficiently characteristic:

Example. 1

7 7 varying between '750 F. and -785"F., and under pressuresvarying between 4300 pounds per square inch and 5100pounds per square inch, for 30 minutes, thermally and catalytically, in the presence of propylene bromide and carbon -dioxide.

The results were as follows:

Yieldof alkylate Per cent of trip- Catalyst boiling at 75 O. tune in alkylate 85 0.,per cent boiling at 75 C.-

' by weight 85 None V 14.7 9:1:1 Pro ylene bromide 35 .1 65:1 Car on dioxide 37. 7 55:1

Amount of cata- Yield of alkylate Per cent triptane lyst, per cent boiling at 75 in alkylate boilby volume of C.85 (3., per mg at 75 0.-

charge cent by-weight 85 C.

The results show that the catalytic efiect of carbon dioxide reaches a maximum at concentrations of about 7% to 8%.-

Example 3 lowing hexanes was obtained:

Per cent by weight (1) Neohexane fraction containing: (a) -2,2-d1methylbutane Eneohexane) 95 (b3 2,3-dimethylbutane diisopropyl) r 2 (c Other hexanes balance and boiling at 40 0-"55 C. 30.1 (2) Diisopropyl fraction containing:

(a) 2,2-dimethylbutane (nephexane) 10 (b) 2,3-dimethylbutane (di1sopropyl) (c) Other hexanes balance and boiling at 55 O.65 O. 15. 2

Total hexanes in alkylate 45. 3

Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the i tion, as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

I'claim: f

1. In the process of alkylating a parafiinic hydrocarbon with an ol'efinic hydrocarbon, which includes reacting a paraffinic hydrocarbon with an olefinic hydrocarbomin a reaction zone under alkylating conditions, in the presence of catalytic material, and controlling the concentration of the olefinic hydrocarbon: so that alkylationis the principal reaction; the improvement which comprises reacting said paraflinichydrocarbon with 5 said olefinic hydrocarbon, in a reaction 'zone under alkylating conditions, in the presence of carbon dioxide. V .2. The process of'manufacturing high-octane motor fuel, which comprises reacting alight iso- 10 parafiinic hydrocarbon with a light olefinic hydrocarbon, in a reactionzone under alkylating conditions, in the presence of carbon dioxide, and controlling the concentration of the light olefinic hydrocarbon so that alkylation is the principal reaction.

3. The process which comprises reacting isobutane with propylene, in a reaction zone under alkylating conditions including temperatures varying between about 775 F. and about 825 F. and pressures of at least 2500 pounds per square inch, in the presence of carbon dioxide, and controlling the concentration of propylene so that alkylation is the principal reaction.

4.'Th process of manufacturing neohexane, which comprises reacting isobutane with ethylene, in a reactionrzone under alkylating conditions including temperatures varying between about 650 F. and about 825 F. and; pressures of at least 1500 pounds per square inch, in the presence of carbon dioxide, and controlling the concentration of the ethylene so that alkylation is the principal reaction. g

5. In the process of alkylating an isoparafilnic hydrocarbon with an olefinic hydrocarbon, which includes reacting an isoparaflinic hydrocarbon with an olefim'c hydrocarbon, in a reaction zone under alkylating conditions, in the presence of catalytic material, and controlling the concen-- tration of the olefinic hydrocarbon so that alkylation is the principal reaction; the improvement which comprises reactingsaid isoparafiinic hydrocarbon with said olefinic hydrocarbon, in a reaction zone under alkylating conditions including temperatures varying between about 590 F. and about 850 F.- and pressures of at least 500 pounds per squareinch, in the presence of carbon dioxide. i N

6. The process of manufacturing highoctane motor fuel, which comprises reacting a normally 7 gaseous isoparaifinic hydrocarbon with 2. normally gaseous olefinic hydrocarbon, in a reaction zone underalkylating conditions including temperatures varying between about 650-F. and aboutf825 F. and pressures of at least 1500 pounds per square inch, in the presence of carbon dioxide, and controlling the concentration of the normally gaseous olefinic hydrocarbon so that alkylation is the principal reaction;

7. In the process of manufacturing high-octane motor fuel by alkylating a normally gaseous isoparafiinic hydrocarbon with a normally gaseous olefinic hydrocarbon, which includes reacting said normally gaseous isoparafiinic hydro- 6 carbon with said normally gaseous olefinic hydrocarbon, in a reaction zone under alkylating conditions, in the presence of catalytic material, and controlling the concentration of the normally gaseous olefinic hydrocarbon so that al- 70 kylation is the principal reactionythe improvement'which comprises reacting said normally of manufacturing triptana,

9 about 850 F. and pressures of at least 2500 pounds per squar inch, in the presence of carbon dioxide.

8. In the process of alkylating a paraifinic hydrocarbon with an olefinic hydrocarbon, which includes reacting a paraffinic hydrocarbon with an olefinic hydrocarbon, in a reaction zone under alkylating conditions, in the presence of catalytic material, and controlling the concentration of the olefinic hydrocarbon so that alkylation is the principal reaction; the improvement which comprises reacting said paraflinic hydrocarbon with said olefinic hydrocarbon, in a reaction zone under alkylating conditions, in the presence of an alkylation catalyst consisting essentially of carbon dioxide, in amounts varying between about 3% and about 20% with respect to the total volume of the charge.

9. The process of manufacturing high-octane motor fuel, which comprises reacting a light isoparafiinic hydrocarbon with a light olefinic hydrocarbon, in a reaction zone under alkylating conditions including temperatures varying between about 590 F. and about 850 F. and pressures of at least 500 pounds per square inch, in the presence of an alkylation catalyst consisting essentially of carbon dioxide in amounts varying between about 3% and about 20% with respect to the total volume of the charge, and controlling the concentration of the light olefinic hydrocarbon so that alkylation is the principal reaction.

10. In the process of manufacturing highoctane motor fuel by alkylating isobutane with propylene, which includes reacting said isobutane and said propylene, in a reaction zone under alkylating conditions, in the presence of catalytic material, and controlling the concentration of the propylene so that alkylation is the principal reaction; the improvement which comprises reacting said isobutane with said propylene, in a reaction zone under alkylating conditions including temperatures varying between about 750 F. and about 850 F. and pressures of at least 2500 pounds per square inch, in the presence of an alkylation catalyst consisting essentially of carbon dioxide, in amounts varying between about 3% and about 20% with respect to the total volume of the charge.

11. The process of manufacturing triptane,

which comprises reacting isobutane with propylene, in a reaction zone under alkylating conditions including temperatures varying between about 775 F. and about 825 F. and pressures of at least 2500 pounds per square inch, in the presence of an alkylation catalyst consisting essentially of carbon dioxide in amounts varying between about 6% and about 9% with respect to the total volume of the charge, and controlling the concentration of the propylene so that alkylation is the principal reaction.

12. The process of manufacturing neohexane, which comprises reacting isobutane with ethyl ene, in a reaction zone under alkylating conditions including temperatures varying between about 650 F. and about 825 F. and pressures of at least 1500 pounds per square inch, in the presence of an alkylation catalyst consisting essentially of carbon dioxide in amounts varying between about 6% and about 9% with respect to the total volume of the charge, and controlling the concentration of the ethylene so that alkylation is the principal reaction.

13. The process of alkylating a paraifinic hydrocarbon with an olefinic hydrocarbon, which comprises contacting said paraffinic hydrocarbon and said olefinic hydrocarbon in gaseous phase and in a reaction zone under alkylating conditions, with an alkylation catalyst consisting essentially of carbon dioxide, and controlling the concentration of the olefinic hydrocarbon so that alkylation is the principal reaction.

14. The process of manufacturing high-octane motor fuel, which comprises contacting a light isoparaffinic hydrocarbon and a light olefinic hydrocarbon in gaseous phase and in a reaction zone under alkylating conditions, with an alkylation catalyst consisting essentially or carbon dioxide, and controlling the concentration of the light olefinic hydrocarbon so that alkylation is the principal reaction.

15. The process of manufacturing triptane, which comprises contacting isobutane and propylene in gaseous phase and in a reaction zone under alkylating conditions, with an alkylation catalyst consisting essentially of carbon diomde, and controlling the concentration of the propylene so that alkylation i the principal reaction.

WILLIAM A. STO'VER. 

